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Chapter 5 Published Results 5.B.5. Conclusions We have prepared the three dimeric, sandwich-type tungstogermanates [Cu 3 (H 2 O)(B-β- GeW 9 O 33 (OH))(B-β-GeW 8 O 30 (OH))] 12– (29), [Co(H 2 O) 2 {Co 3 (B-β-GeW 9 O 33 (OH))(B-β- GeW 8 O 29 (OH) 2 )} 2 ] 20– (30) and [Mn(H 2 O) 2 {Mn 3 (H 2 O)(B-β-GeW 9 O 33 (OH))(B-β- GeW 8 O 30 (OH))} 2 ] 22– (31) in simple, one-pot reactions using aqueous, buffered pH 4.8 medium. All three polyanions 29-31 have been fully characterized by single-crystal X-ray diffraction, FTIR, elemental analysis, and thermogravimetric analysis. The magnetic properties of K-29, K-30 and K-31 have been also studied. We used Cu 2+ , Co 2+ or Mn 2+ to [γ- GeW 10 O 36 ] 8– ratios of 1.5:1 for the synthesis of 29-31. Our results demonstrate that the reactivity of [γ-GeW 10 O 36 ] 8– with 3d metal ions in an aqueous acidic medium is similar to that of its silicon analogue [γ-SiW 10 O 36 ] 8– . Both species can easily rearrange to different isomers of trilacunary “XW 9 ” and tetralacunary “XW 8 ” fragments which coordinate to the d-block metal ions, resulting in sandwich-type assemblies. We have shown that [γ-GeW 10 O 36 ] 8– is a highly flexible lacunary POM precursor which can adjust to the specific coordination requirements of the respective type of transition metal ion (e.g. Cu 2+ vs Co 2+ ). We believe that 29-31 could also be interesting for homogeneous or heterogeneous oxidation catalysis applications. Currently, we are exploring the reactivity of [γ-GeW 10 O 36 ] 8– with other d- and f- block metal ions. 211
Chapter 5 Published Results 5.B.6. References [1] J. J. Berzelius, Pogg. Ann. 1826, 6, 369. [2] a) M. T. Pope, Heteropoly and Isopoly Oxometalates; Springer: Berlin, 1983; b) M. T. Pope, A. Müller, Angew. Chem., Int. Ed. Engl. 1991, 30, 34; c) M. T. Pope, In Comprehensive Coordination Chemistry II; J. A. McCleverty, T. J. Meyer, Eds.; Elsevier Ltd.: Oxford, U.K., 2004; d) C. L. Hill, In Comprehensive Coordination Chemistry II; A. G. Wedd, Ed.; Elsevier Ltd.: Oxford, U.K., 2004. [3] a) Polyoxometalates: From Platonic Solids to Anti Retroviral Activity; M. T. Pope, A. Müller, Eds.; Kluwer: Dordrecht, 1994; b) Chem. Rev. 1998, 98, 1-389 (Special Thematic Issue on Polyoxometalates); c) Polyoxometalate Chemistry: From Topology Via Self- Assembly to Applications; M. T. Pope, A. Müller Eds.; Kluwer: Dordrecht, 2001; d) Polyoxometalate Chemistry for Nano-Composite Design; T. Yamase, M. T. Pope, Eds.; Kluwer: Dordrecht, 2002; e) Polyoxometalate Molecular Science; J. J. Borrás-Almenar, E. Coronado, A. Müller, M. T. Pope, Eds.; Kluwer: Dordrecht, The Netherlands, 2003; f) M. Vazylyev, D. Sloboda-Rozner, A. Haimov, G. Maayan, R. Neumann, Top. Catal. 2005, 34, 93. [4] a) R. Sessoli, D. Gatteschi, A. Caneschi, M. A. Novak, Nature, 1993, 365, 141; b) P. Gambardella, S. Rusponi, M. Veronese, S. S. Dhesi, C. Grazioli, A. Dallmeyer, I. Cabria, R. Zeller, P. H. Dederichs, K. Kern, C. Carbone, H. Brune, Science, 2003, 300, 1130; c) J. R. Long, in Chemistry of Nanostructured Materials, P. Yang, Ed. World Scientific Publishing, Hong Kong, 2003, pages 241; d) M. Bode, O. Pietzsch, A. Kubetzka, R. Wiesendanger, Phys. Rev. Lett., 2004, 92, 067201; e) D. Gatteschi, R. Sessoli, J. Villain, Molecular Nanomagnets, Oxford Univ. Press, Oxford, 2006. [5] a) T. Yamase, B. Botar, E. Ishikawa, K. Fukaya, Chem. Lett. 2001, 56; b) N. Laronze, J. Marrot, G. Hervé, Inorg. Chem. 2003, 42, 5857; c) T. M. Anderson, W. A. Neiwert, K. I. Hardcastle, C. L. Hill, Inorg. Chem. 2004, 43, 7353; d) S. Nellutla, J. van Tol, N. S. Dalal, L. 212
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